C10-c13 hydrocarbyl substituted pyridine compounds

ABSTRACT

NOVEL NITROGEN HETEROCYCLIC COMPOUNDS DEFINED BY THE STRUCTURE:   2-(A1),4-(A2),(R1)M-PYRIDINE   WHEREIN R1 REPRESENTS C1-C3 LOWER ALKYL AND M IS A INTEGER RANGING FROM ZERO UP TO 2; WHEREIN ONE A1 OR A2 IS A MOIETY SELECTED FROM THE GROUP CONSISTING OF CYCLODODECEN - 3 - YL-METHYL, 2-PINEN-10-YL-METHYL, 4,.8DIMETHYL - 3.7 - HONADIENYL, 3-METHYL - 6 - I-PROPYL-2CYCLOHEXENYL-METHYL, AND 1,4.8-TRIMETHYL -3.7 - NONADIENL-YL: AND THE OTHER OF A1 OR A2 IS R1 OR HYDROGEN.

United States Patent 3,716,543 (r -c HYDROCARBYL SUBSTITUTED PYRIDINECOMPOUNDS John B. Hall, Rumson, N..l., assignor to International Flavorsand Fragrances Inc., New York, NY.

No Drawing. Continuation-impart of application Ser. No. 854,787, Sept.2, 1969. This application July 28, 1970, Ser. No. 59,027

Int. Cl. C07d 31/20 US. Cl. 260290 V 9 Claims ABSTRACT OF THE DISCLOSURENovel nitrogen heterocyclic compounds defined by the structure:

wherein R represents C C lower alkyl and m is an integer ranging fromzero up to 2; wherein one of A or A is a moiety selected from the groupconsisting of cyclododecen 3 yl-methyl, Z-pinen-lO-yl-methyl, 4,8-dimethyl 3,7 nonadienyl, 3-'nethyl 6 i-propyl-2- cyclohexenyl-methyl,and 1,4,8-trirnethyl 3,7 nonadienl-yl; and the other of A or A is R orhydrogen.

CROSS-REFERENCE TO RELATED APPLICATIONS This application is acontinuation-in-part of US. application for Letters Patent No. 854,787filed Sept. 2, 1969, and issued on June 16, 1972, as US. Pat. No.3,669,908.

BACKGROUND OF THE INVENTION There is a continuing search for materialshaving desirable fragrance and organoleptic properties. Such materialsare sought either to replace costly natural materials or to provide newfood flavors, tobacco flavors, fragrances, perfume types or flavornuances which have not heretofore been available.

Especially desirable qualities for substances having interestingfragrances and flavors are stability in a wide variety of perfumedarticles, perfume compositions and foodstuffs, ease of manufacture,intensity and pleasantness of aroma, and intensity and pleasantness offlavor.

THE INVENTION The invention comprises the novel products, as well asnovel processes according to which such products are manufactured, thespecific embodiments of which are described hereinafter by way ofexample and in accordance with which it is now preferred to practice theinvention.

Briefly, the present invention provides novel alkadienyl-, cycloalkenyl,cycloalkylidenealkyl, cycloalkylal-kenyl and cycloalkenylalkylsubstituted heterocyclic nitrogen com- 3,715,543 Patented Feb. 13, 1973"ice pounds, particularly pyridines and pyrazines having the generalformulae:

wherein m is l, 2, 3 or 4; and wherein n is 1, 2 or 3; wherein the Rgroup (or groups) is (are) substituent(s) on one or more of the carbonatoms which are part of the heterocyclic rings; wherein R is eitherhydrogen or alkyl including but not limited to, methyl, ethyl, propyl,butyl, pentyl and heptyl; wherein each of R and R are separatelyhydrogen, methyl or ethyl; wherein the sum of the number of carbon atomsin R and R (taken together) is from 0 up to 2; wherein the sum of thenumber of carbon atoms in R R and R '(taken together) is from 10 up to13; wherein R is C-9 C-lO, C11 or C-12 alkadienyl-, cycl0alkenyl-,cycloalkyialkenyl-, cycloaikylideneal kyland cycloal-kenylakyl; whereinR is hydrogen, methyl or ethyl; wherein one of R and R is al'kenyl andthe other of R and R is hydrogen or lower allryl, or R and R takentogether form a cycloalkyl group; wherein the sum of the number ofcarbon atoms in R R and R7 is from eight up to eleven; wherein R and Reach represents hydrogen or lower alkyl, including but not limited tomethyl, ethyl, n-propyl, i-propyl, n-butyl and n-pentyl; wherein E and Geach represents a chain of alkyl substituted or unsubstituted carbonatoms completing a cycloalkenyl ring, including but not limited tomonocyclic and bicyclic moieties; wherein the sum of the number ofcarbon atoms in R and E (including al'kyl substituents on thecycloalkenyl' ring, if any) is from 8 up to 11, and the sum of thenumber of carbon atoms is R R R and G (including alkyl substituents onthe cycloal kenyl ring, if any) is from 8 up to 11.

Perfume, flavor and tobacco, flavor and fragrance modifying materialscontaining such substituent pyridines and pyrazines are alsocontemplated herein.

The present invention further relates to compositions useful in alteringthe organoleptic characteristics of a foodstuff or tobacco. Moreparticularly, this invention has to do with, interalia, the use of thenovel alkadienyl, cycloalkenyl, cycloalkylalkenyl, cycloalkylidenealkyl,and cycloalkenylalkyl-substituted heterocyclic ntirogen compounds of theinvention to alter the flavor of foodstuffs and tobacco.

The term alter in its various forms is used herein to mean the supplyingor imparting a flavor character or note to an otherwise bland,relatively tasteless substance, or augmenting the existing flavorcharacteristic where a natural flavor is deficient in some regard, orsupplementing the existing flavor impression to modify its quality,character or taste.

The term foodstuff as used herein includes both solid and liquidingestible materials which usually do, but need not, have nutritionalvalue. Thus, foodstuffs include meats, gravies, soups, conveniencefoods, beverages, dairy products candies, vegetables, cereals, softdrinks, snacks and the like.

Seafood-like, potato and spice such as cinnamon flavored foodstuffs arevery popular, and a great deal of elfort has been devoted to thepreparation of materials which have a seafood-like, potato or naturalspice flavor as well as to improve the spicy, fish-like or potatoflavors of certain types of natural materials.

As used herein, seafood-like flavors will be understood to mean flavorsassociated with marine animals including crustaceans such as shrimp,lobster and the like; mollusks such as oysters, clams, and the like; andparticularly fish including smoked fish, dried fish, salted fish, andthe like. Thus, at levels as low as 50 parts per billion, several of thenitrogen heterocyclic compounds of the invention begin to impart a verylight, almost indefinable, sensation in aqueuos solution. As the levelis increased to one part per million (p.p.m.) a definite pleasant saltwater fish-like character is imparted to an aqueous solution. As thelevel reaches 2 p.p.m., a definite, good characteristic fish-like flavoris obtained and this flavor persists up through levels of p.p.m. andbeyond, where the substance leaves a light, lingering aftertaste.

In the past, it was found that substitute spice (such as cinnamon)flavoring materials lacked certain supporting qualities [c.g. woodinessor bark-like] characteristics found in quality spice (such as cinnamonand pimentos). It was further found that substitute potato flavoringmaterials lacked certain green characteristics found in the flavor ofnatural potato and the products made from such materials were deficientin flavor and/ or aroma. It was further found that many tobaccoproducts, particularly after processing thereof lacked adequate flavor.In addition, it was found that many proteinaceous products such as fishprotein products prepared according to the processes set forth in FrenchPat. 1,540,106, US. Pat. 3,437,489 or British Pat. 1,157,- 415 aredevoid of the flavors required to make them palatable, e.g. give them ahigh quality seafood-like flavor.

In accordance with this invention, it has been found that novel tobacco,foodstutf and flavoring compositions having seafood-like, spice (such ascinnamon) or tobacco-like characteristics found in quality fish, spiceand tobacco flavors may be provided by the utilization of at least oneof the novel compounds of this invention. It has also been found thatnovel potato flavoring compositions having green characteristics foundin natural potato may be provided by the utilization of at least one ofthe compounds of the invention.

The novel heterocyclic compounds are obtained by one of severalprocesses involving:

1) The reaction of a picoline or higher homologue (at, 13, or '7 methyl,ethyl or propyl pyridine) or a methyl, ethyl, or propyl pyrazine withC-9, C10, C-ll or Cl2 conjugated cycloalkenylalkanes, conjugated cycloalkadienes or alkatrienes (having two of its double bonds conjugated) orC9, 0-10, Cl1 o-r C12 al'kadienyl, cycloalkylalkenyl, cycloalkenyl, orcycloalkylidenealkyl, or cycloalkenylalkyl halides, tosylates, mesylatesor similar sulfonic acid esters;

(2) The reaction of an alkyl-substituted or unsubstituted pyrazine orpyridine with an aldehyde or ketone which also may contain acarbon-carbon double bond, in the presence of mercuric chloride andaluminum or magnesium, followed by hydrolysis, and dehydration and, ifnecessary, hydrogenation;

(3) The reaction of a pyridine or pyrazine grignard with an aldehyde orketone which may contain a carboncarbon double bond, followed byhydrolysis, dehydration and, if necessary, hydrogenation; and

(4) The reaction of a lithium picoline or a lithium methyl pyrazine withan aldehyde or ketone which may contain a carbon-carbon double bond,followed by hydrolysis, dehydration, and, if necessary, hydrogenation;as more fully described hereinafter.

More specifically, this invention contemplates C-lO, C-1 1, C-12 or 0-13alkadienyl, cycloalkenyl, cycloalkylalkenyl, cycloalkylidenealkyl andcycloalkenylalkyl nitrogen heterocyclic compounds which can additionallycon tain one or more alkyl substituents on a ring carbon atom.Desirably, the alkyl substituent on the heterocyclic ring is a loweralkyl group and it preferably contains from one to about three carbonatoms. Thus, the invention encompasses, but is not limited to thefollowing compounds:

2-(4,8-dodecadienyl)pyridine 4- (4,8-undecadienyl) pyrazine 2-(l,4,8-trimethyl-3,7-nonadienyl) pyridine 2-( l-methyl-4,S-dodecadienyl)pyridine 2- (4,8-dimethyl-3 ,7-nonadienyl pyridine3-(4,8-dimethyl-3,7-nonadienyl)pyridine 4- (4,8-dimethyl-3 ,7-nonadienylpyridine 2-(4,8-dimethyl-3,7-nonadienyl)pyrazine3-ethyl-6-(4,8-dimethyl-3,7-nonadienyl pyridine 2-ethyl-4-(4,8-dimethyl-3,7-nonadienyl) pyridine3-ethyl-4-(4,8-dimethyl-3,7-nonadienyl)pyridine 2- (cyclododecen-S-ylpyridine 4-(Z-pinen-l0-yl-methyl)pyridine 2-(2-pinen-1 O-yl-methyl)pyridine 4-(2-pinen-10-yl-methyl)-2-n-propyl pyridine2-ethyl-5-(4,8-dimethyl-3,7-nonadienyl) pyrazine(Z-cyclododecen-l-yl)pyrazine 4- (2-cyclododecen- 1-yl-methyl)pyridine I5-(4,8-dimethyl-3,7nonadienyl)-2-n-propyl pyrazine The compounds of thisinvention may occur in various isomeric forms such as cis-cis,trans-trans, cis-trans and trans-cis and such isomeric forms arecontemplated within the scope of the invention and included in theformulae shown.

It has been found that, unlike known nitrogen heterocyclic compoundssuch as u-(3-phenyl propyl)pyridine [described by Arctander, Perfume andFlavor Chemicals, vol. II, No. 2601] those compound described in US.Pat. 2,427,286; those described in Chumekov et al. (Chem. Abstracts63:5594y) Ukr. Khim. Zhz3l (5) 50613 (1965); and those described inPines et al., J. Org. Chem. 32, 3183, 1967, the compounds of thisinvention themselves possess qualities (depending upon their particularstructure, e.g. position and/ or size of ring-substituent(s)) associatedwith (1) aromas including seashore or fishlike aromas or green pepper,potato, valuable citrus undertones such as petitgrain oil-like,corianderoillike; or berry fruit, green or woody-amber aromas; or (2)flavor notes including those useful in imparting seafood-like qualitiesto foodstuffs, those useful in potato such as green notes as well asthose useful in spice flavors including woody notes. These flavor andfragrance qualities particularly adapt the novel nitrogen heterocycliccompounds of this invention for incorporation into perfume andfragrance-modifying compositions having desirable seashore,green-peppery, berry or vary the organoleptic or odor impression of aflavor or perfume so as to impart either such notes as seashore orwoody-amber notes (to the perfume composition), or such notes as greenor seafood-like or spice-like notes to the flavor composition.

It will be appreciated by those skilled in the art from the presentdisclosure, that the fragrance character of the finished perfumecompositions can be tailored to specific uses, as more fully describedhereinafter; and that the flavor character of the finished flavorcompositions can be tailored to specific uses in foodstufis, beveragesor tobacco as more fully described hereinafter.

A number of dilferent starting materials can be utilized to produce thenovel nitrogen heterocyclic compounds of this invention.

In one method of this invention a methyl pyridine (picoline) ormethylpyrazine is reacted with a -10 alkadienyl or cycloalkenyl orcycloalkylalkenyl or cycloalkylidenealkyl, or cycloalkenylalkyl halide,tosylate or mesylate or similar C-lO sulfonic acid ester in the presenceof an alkali metal or alkali metal amide or hydride to form thecorresponding C-ll alkadienyl or cycloalkenyl or cycloalkylalkenyl orcycloalkylidenealkyl or cycloalkenylalkyl pyridine or pyrazine.Similarly, ethyl-, n-propyl, or i-propyl-pyridines or pyrazines arereacted with 0-10 alkadienyl halides, tosylates or mesylates or similarC-lO alkadienyl sulfonic acid esters in the presence of an alkali metalor alkali metal amide or hydride to form the corresponding C-12 or C-13alkadienyl pyridine or pyrazine. In addition, methyl, ethyl or propylpyridines or methyl, ethyl or propyl pyrazines may be reacted With C-9,C-lO, C-ll or 0-12 alkadienyl or cycloalkenyl or cycloalkenylalkyl orcycloalkylalkenyl or cycloalkylidenealkyl halides, tosylates, mesylatesor similar alkyl sulfonic acid esters. The procedure is simiar to thatset forth in Brown and Murphey, J. Am. Chem. Soc., 73, 3308 (1951).

Examples of C-9, C-l0, C-ll and C-l2 alkadienyl-, or cycloalkenyl orcycloalkenylalkyl or cycloalkylalkenyl or cycloalkylidenealkyl halides,tosylates and mesylates useful as reactants and contemplated within thescope of this invention are myrtenyl chloride; 2,6-undecadienylchloride; myrcene hydrochloride; 3-chlorocyclododecene;2,6-nonadienylchloride; cyclohexylidene-nbutyl bromide; myrcenehydrobromide; geranyl chloride; geranyl bromide; neryl chloride, nerylbromide, geranyl tosylate, and geranyl mesylate. The structures ofseveral of the aforementioned halides are set forth in US. Pat.2,822,323.

In another method of this invention a methyl, ethyl, or propyl pyridineis reacted with a C-9, C-l0, C-ll or C-12 alkatriene having tWo of itsdouble bonds conjugated or a conjugated cycloalkadiene or a conjugatedcycloalkenylalkene in the presence of an alkali metal such as sodium,potassium or lithium metal to form the alkadienyl, cycloalkenyl orcycloalkenylalkyl pyridines and pyrazines of this invention. Suitablealkatrienes include myrcene [3-methylene-7-methyl-1,6-octadiene];l,4,6-un-- decatriene; 2,3,7-trimethyl-2,5,7-nonatriene; and2,5,7-trimethyl-2,5,7-octatriene. Suitable cycloalkadienes andcycloalkenyl alkenes include 1-vinyll-cyclodecene; 1,3-cycloundecadiene;3-methylene-cyclodecene-1; 3-methylene cyclododecene-l;2,4,G-trimethyl-cyclohexa 1,3 diene; verbenene having the structure:

A -p-menthadiene; u-phellandrene; nopadiene; 1,3-cyclododecadiene andfi-phellandrene having the structure:

The procedure is similar to that used by Chumakov et al. in Ukr. Khim.Zh. 31 506-13 (1965).

As used herein structures such as those set forth in the precedingparagraph [wherein methyl (CH groups and methylene (CH groups areincluded as part of the structure] show these methyl and methylenegroups simply as straight lines, thus:

is intended to mean:

/a7\ 1 Ce Examples of alkyl pyridines and alkyl pyrazines useful asreactants and which are contemplated within the scope of the processesof this invention are TABLE I Alkadienyl halide mesylate or tosylate;alkatriene: Nitrogen heterocyclic cycloalkadiene: or compoundeycloalkenylalkane Reaction product 2 rnethyl-pyridineCyclododecen-3-yl- 2(cyclododecen-3-ylc loride. methyDpyridine.4-methyl-pyridme Myrtenyl chloride..- 4-(2-pilim-l0-yl-methyl) pyn ne.Z-methyl-pyridine do 2-(2-pigen-10-yl-methyl) DY n 2-n-propyl-4-methylMyrtenyl br0mlde 2-n-propyl-4(2-pinen-10- pyridine l-rnethyl) pyridine.

Y 2,5-diethyl pyrazine-.. 1-chloro-3,7-di-2-ethyl-5-(4,8-dimethylrinethyl 2,6-0cta- 3,7-nonadienyl) pyrazlne.

iene. Methyl pyrazine 3-methylene-1-cyclo- (2-cyclodecen-l-yl-methyl)decene. pyrazine. 4-methyl-pyridine 1-chloro-3,7-dirnethy4-(4,8-dimethyl-3,7-non- 2,6-octadiene. adienyl)pyridine.2-methyl-pyrldine. 4,8-dimethyl-l.3,7- 2-(4,8-dlmethyl$,7-n0noctatriene.adienyl)pyridine. 5-ethyl-2-methyl- 1-chl0ro3,7-di-2-ethyl-5-(4,8-dimethylpyridine. ririethyl-zfi-octa-3,7-nonadienyl)pyridine.

ene.

Z-methyl-pyridlnefi-Phellandrene- 2-(3-methyl-6-i-propyl-2-eyclohexenylmethyl pyridine.

Do Verbenene 2-(2-plnen-l0-yl-methyl) pyridine.

The reactants are carried out preferably at atmospheric pressure attemperatures of the order of 0 C. up to C. It is preferred to use anexcess of the alkyl pyridine or alkyl pyr-azine compound; of the orderof 10-150%. The reactions are carried out in the presence of an alkalimetal or alkali metal amide of hydride, such as sodium metal, potassiummetal, lithium metal, sodium amide, sodium hydride, potassium amide orlithium amide.

At the completion of any of the foregoing reactions the reaction mixtureis preferably poured into water and then purified. The novel compoundsare recovered from the reaction mixture by means of suitable techniquessuch as distillation, extraction, chromotographic techniques and thelike. It has been found that fractional distillation under vacuum is adesirable way to obtain the pure compounds from the reaction mixtures.

The instant reactions are summarized generally as follows:

An additional synthesis technique for production of the C-lO, C-ll, C-12and C-13 alkadienyl-, cycloalkylalkenyl, cycloalkenyl andcycloalkylidenealkyl and cycloalkenylalkyl pyridines and pyrazines ofthis invention involves the reaction of a pyridine or pyrazine grignardwith a Cl0, C-ll, C-l2 or C-13 alkenal, alkenone, cycloalkylalkanone,cycloalkenyl-alkanal, alkenyl-cycloalkanone, alkylidene-cycloalkanone,epoxy cycloalkane or cycloalkenone; followed by hydrolysis andsubsequent dehydration; and if the case required it, subsequenthydrogenation. Cycloalkanones are also suitable reactants.Epoxycycloalkenes, alkadienals, cycloalkylalkenones,cycloalkenylalkanones, alkadienones and cycloalkadienalkanals andcycloalkadienones may also be used and an additional hydrogenation stepis necessary in these cases in order to yield the desired novel productsof this invention.

Suitable pyridine and pyrazine grignard materials are: a pyridylmagnesium chloride tetrahydrofuran complex; 'y pyridyl magnesiumchloride tetrahydrofuran complex; pyrazine magnesiumchloride-tetrahydrofuran complex; 5 methylpyrazine 2 magnesiumchloridetetrahydrofuran complex; and S-ethyl pyridine 2 mag nesiumchloride tetrahydrofuran complex, produced via the process described byRamsden in US. Pat. 2,959,589 issued on Nov. 8, 1960. ,1

An example of a suitable alkenal is citronellal' [3,7-dimethyl-d-octen-l-al]. An example of a suitable cycloalkenylalkanal isphellandral having the structure:

An example of a suitable cycloalkylalkanone is tetrahydroionone havingthe structure:

An example of a cycloalkenylalkanone An example of a suitable alkenoneis S-decen-Z-one having the structure:

Examples of epoxy cycloalkanes suitable for utilization in reacting withpyridine or pyrazine grignards are: 3,4-epoxycarene having thestructure:

cyclododecane epoxide and cyclodecane epoxide.

Examples of cycloalkanones suitable for use in reacting with pyridine orpyrazine grignards are: menthone and carvomenthone having thestructures, respectively:

carone and caronone having the structures, respectively:

pinocamphone and verbanone having the structures, respectively:

fenchone and camphor having the structures, respectively:

thujone having the structure:

An example of a suitable alkenylcycloalkanone is isodihydrocarvonehaving the structure:

Examples of suitable alkylidene cycloalkanones are pulegone (dextro),d-p menth-4(8)-en-3-one], having the structure:

| and pinocarvone having the structure:

Examples of suitable cycloalkenones are piperitone having the structure:

and verbenone having the structure:

M l and umbellulone having the structure:

An example of a suitable epoxy cycloalkene is 7,8-epoxyl-cyclododecenehaving the structure:

Suitable hydrolysis reagents are mineral acids such as dilutehydrochloric acid and dilute sulfuric acid. Dehydration may beaccomplished by heating the hydrolyzed materials in the presence of suchmineral acids.

The instant reaction sequence is summarized generally as follows:

wherein X and X can form a cycloalkylene ring or one of X or Xrepresents alkenyl or cycloalkenyl and the other X or X represents alkylor hydrogen. A specific example of the instant reaction is as follows:

MgCl

The C-10, C-l1, C-lZ or C-l3 alkadienyl-, cycloalkenyl,cycloalkylidenealkyl, cycloalkylalkenyl and cycloalkenylalkyl pyridinesand pyrazines of this invention, produced as indicated above, may beused as such, or may be further treated in order to isomerize thecompounds as by (1) shifting the carbon-carbon double bond (or bonds, asthe case may be) located in the hydrocarbon moiety which is bonded tothe heterocyclic nitrogen moiety; or by (2) cracking the hydrocarbonring moiety [in the case of such compounds as 2-(2-pinen-10-yl-methyl)pyridine].

The shifting of the carbon-carbon double bond (or bonds) may beaccomplished by use of either (a) catalytic quantities of palladium oriron carbonyl; (b) Lewis acids such as excess BF or EH in anhydrousmedia [as taught by Brown et al., I. Am. Chem. Soc., vol. 89, pg. 567(Feb. 1, 1967)] and (c) potassium-t-butoxide in dimethyl sulfoxide.

The cracking reaction is accomplished by subjecting such materials as2-(Z-pinen-l0-yl-methyl)pyridine to temperatures in the range of 250500C.

Thus, for example the following cracking reaction takes place:

Subsequent hydrogenation of this product yields:

thereby producing another, useful product of this invention.

The 0-10, 0-11, C-12 and C-13 alkadienyl-, cycloalkenyl,cycloalkylalkenyl, cycloalkylidenealkyl and cycloalkenylalkyl pyridinesand pyrazines produced according to this invention are olfactory and/ororganoleptic agents and can be incorporated into a wide variety ofcompositions which, when added thereto in small quantities of about oneor two percent will be enhanced by their property of impartingadditional seashore, fishlike, green-pepper, woody-amber, green orberryfruit notes to the fragrance or imparting additional seafood-like,spice, or green notes to the flavor. The materials bring to perfumery anew dimension in seashore notes or green, woody-amber, or berry fruitnotes different from those of existing materials now in use and tofoodstuff flavorings a new dimension in green, spice, and seafood-likenotes different from those notes in existing materials now in use.

An additional synthesis technique for the production of -10, (3-11, 0-12and C-13 alkadienyl, cycloalkenyl, cycloalkyl alkenyl,cycloalkylidenealkyl and cycloalkenylalkyl pyridines and pyrazines ofthis invention involves the reaction of a 0-10, 0-11, (3-12 or 0-13cyclic ketone; or a (3-10, C-11, 0-12 or C-13 alkenone of the formula:

C=O Z Cz wherein Z is methyl or ethyl and 2; represents an alkenylmoiety; or a C-lO, C-1 1, C-12 or 0-13 cycloalkyl alkenone of theformula:

wherein A represents cycloalkyl and B represents an alkenylenyl and Z ismethyl or ethyl, the sum of the number of carbon atoms in A B and Zbeing from nine up to twelve; or a C-10, C-ll, (3-12 or (3-13cycloalkenylalkanone of the formula:

wherein A represents cycloalkenyl, B represents alkyl and 2,, representsmethyl or ethyl with pyridine or pyrazine in the presence of aluminum ormagnesium metal turnings and mercuric chloride in order to form analcohol. Dehydration of the alcohol yields the (3-10, (2-1 1, (3-12 orC-l3 alkadienyl, cycloalkenyl, cycloalkenylalkyl, cycloalkylidenealkyland cycloalkylalkenyl pyridine or pyrazines of the instant invention. Inthe alternative, pyridine or pyrazine may be reacted as above with C-lO,C-ll, C-l2 or C-l3 alkadienones of the formula:

wherein Z is methyl or ethyl and Z is an alkadienyl moiety containingfrom seven to ten carbon atoms and not containing allenic unsaturation;cycloalkenylalkanones or cycloalkylalkenones of the formula:

wherein Z; is methyl or ethyl and Z is cycloalkylalkenyl,cycloalkenylalkyl or cycloalkylidenealkyl containing from seven up toten carbon atoms. In this latter situation bydrogenation is necessarysubsequent to the dehydration step in order to yield the desiredproducts for the instant invention. Lower adjacent methyl homologues ofthe foregoing ketones may also be reacted with methyl pyridines ormethyl pyrazines, the heterocyclic rings of which may also containadditional alkyl substituents.

Generally, the immediately preceding reaction is illustrated thus:

Z; q Z1 W A specific example of the reaction is as follows:

0 W 0 Mg hydrolysis dehydration 0 --v ----r (prepared by the process ofUS. Pat. 3,420,827) I O The foregoing reaction is described forproducing compounds other than the compounds of this invention by Lochteet al., (I. Am. Chem. Soc., 75; 4477-4481) (1953).

Still a further synthesis technique for the production of C-1 0, C-1 1,C-12 or 0-13 alkadienyl-, cycloalkenyl, cycloalkylalkenyl,cycloalkenylalkyl and cycloalkylidenealkyl pyridines and pyrazines ofthis invention involves the reaction of lithium picolines or lithiummethyl pyrazines with 0-9, C-lO, C-11 and C-l2 alkenals, alkenones,cycloalkanones, cycloalkylalkanones and cycloalkylalkanals, followed byhydrolysis of the resultant lithium salt, dehydration and, if the caserequires it hydrogenation. Suitable lithium picoline compounds include:

a-picoline lithium;

B-picoline lithium;

'y-picoline lithium; 4-methyl-2-lithium-methyl pyridine;4-ethyl-2-lithium methyl pyridine; Z-Iithium-methyl pyrazine;

Suitable carbonyl-containing compounds include:

Citronellal,

Phellandral,

Tetrahydroionone,

S-decen-Z-one,

Isodihydrocarvone,

Pinocarvone,

Piperitone,

Verbenone,

Umbellulone, and

Cyclodec-S-ene-l-one (as prepared by the process of French Pat.1,536,621).

If the case requires it, subsequent to the dehydration step ahydrogenation step is necessary in order to yield the desired novelproducts of this invention. Suitable hydrolysis reagents are mineralacids such as dilute hydrochloric acid or dilute sulfuric acid.Dehydration may be accomplished by heating the hydrolyzed materials inthe presence of the said mineral acids or in the presence of oxalicacid. The nature of the foregoing reaction sequence is discussed byArens et a1. Rec. Trav. Chim. 69, 287- 294 (1950). Hydrogenation may becarried out using hydrogen over a palladium or nickel catalyst.

The instant reaction sequence is summarized as follows:

wherein X and X taken together can form a cycloalkene ring orcycloalkane ring, or one of the X or X groups represents alkenyl,alkadienyl, cycloalkenyl, cycloalkyl, cyclolakylalkyl orcycloalkenylalkyl and the other of the X or X groups represents alkyl orhydrogen. A specific example of the instant reaction is as follows:

OH \m Dehydr. O j N Hydrogenation 14 The preferred reaction conditionsfor reactions of the aforementioned aldehydes and ketones with theaforementioned pyridines, pyrazines, pyridine gn'gnards pyrazinegrignards, picoline-lithium compounds and pyrazine methyl lithiumcompounds are tabulated as follows:

Mole ratio of heterocyelic Concennitrogen tration of Temperacompouud:reactants ture of Mole ratio Heterocyclie carbonyl in solvent reactionof catalyst nitrogen compound compound (M) C.) to reactant Pyridine andpyrazine 1 2: 1-l: 2 0. 5-3. 0 200-250 1:10 Pyridine and pyrazinegn'gnard 2:1-124 0. 1-4 10-40 Picolinedithium and pyrazine methyllithium 5: 11:1 0. 5-3. 0 150 1 Using the Loehte et a1. procedure. 1Using the Areus et al. procedure.

Reactions of the heterocyclic nitrogen grignard compounds with the abovementioned epoxy compounds take place at temperatures in the range of60-80 C.

The heterocyclic nitrogen compounds of this invention can be added toflavor and/or perfume compositions in their pure form or they can beadded to mixtures of materials in flavor and/ or fragrance impartingcompositions to provide a desired organoleptic or fragrance character tobe finished flavor or perfum material (as the case may be). The flavor,perfume and fragrance compositions obtained according to this inventionare suitable in a wide variety of foodstuffs and perfumed articles andcan also be used to improve, enhance, modify, alter or reinforce naturalflavor and fragrance materials. It will thus be appreciated that theheterocyclic nitrogen compounds and mixtures thereof of this inventionare useful as olfactory agents and fragrances or organoleptic agents andflavors.

The term perfume composition is used herein to mean a mixture ofcompounds, including for example, natural oils, synthetic oils,alcohols, aldehydes, ketones, esters, lactones, and frequentlyhydrocarbons which are admixed so that the combined odors of theindividual components produce a pleasant or desired fragrance. Suchperfume compositions usually contain: (a) the main note or the bouquetor foundation-stone of the composition; (b) modifiers which round-offand accompany the main note; (c) fixatives which include odoroussubstances which lend a particular note to the perfume throughout allstages of evaporation, and substances which retard evaporation; and (d)top-notes which are usually lowboiling, fresh-smelling materials.

Such perfume compositions or the novel materials of this invention canbe used in conjunction with carriers, vehicles, solvents, dispersants,emulsifiers, surface-active agents, aerosol propellants, and the like.In perfume compositions, the individual components contribute theirparticular olfactory characteristics, but the overall effect of theperfume composition will at least be the sum of the effect of eachingredient. Thus, the nitrogen heterocyclic compounds of this inventioncan be used to alter the aroma characteristics of a perfume composition,for example, by highlighting or moderating the olfactory reactioncontributed by another ingredient of the compo sition.

The amount of one or more compounds of this invention which will beefiective in perfume compositions depends on many factors, including theother ingredients, their amounts and the effects which are desired. Ithas been found that perfume compositions containing as little as 1.0% byweight of the compounds of this invention, or even less can be used tointensify or augment and enhance various types of fragrance compounds,the odors of which may be desired to be imparted to colognes, perfumes,bath oils and other cosmetic products. The amount employed will dependon considerations of cost, nature of the end product, the effect desiredin the finished product, and the particular fragrance sought. Higherconcentrations (e.g. 4% by weight) of the nitrogen heterocycliccompounds of this invention will intensify the seashore, fishdike,green, woody-amber," green-pepper or berry fruit notes of thecompositions.

The nitrogen heterocyclic compounds disclosed herein can be used in acomposition as an olfactory component of a fragrance which in turn canbe used in perfumes, colognes, bath preparations (such as bath oils andbath salts) and the like. When the alkadienyl, cycloalkenyl,cycloalkylalkenyl, cycloalkylidenealkyl or cycloalkenylalkyl pyridinesor pyrazines of this invention are used in finished perfumed articles,such as the foregoing, they can be used in amounts of 0.04% or lower.

When used to impart, alter, modify or enhance flavors in foodstufis andin tobacco, the novel alkadienyl, cycloalkenyl, cycloalkylalkenyl,cycloalkylidenealkyl or cycloalkenylalkyl-substituted heterocyclicnitrogen compounds of this invention may be employed either singly or inadmixture comprising two or more thereof. In this manner, the processeris afforded means whereby to exploit the beneficial nature of each of aplurality of compounds in a specific instance.

In many instances the optimum balance of flavor is obtained by utilizingmixtures of compounds wherein at least one component comprises anunsubstituted C-lO, -11, 0-12 or C-13 alkadienyl, cycloalkenyl,cycloalkylalkenyl, cycloalkylidenealkyl, cycloalkenylalkyl, pyridine orpyrazine, i.e., contains no substituents on either the pyrazine moietyor the pyridine moiety and the other component comprises at least onesubstituted (3-10, C-ll, C-lZ or 0-13 alkadienyl, cycloalkenyl,cycloalkylalkenyl, cycloalkylidenealkyl or cycloalkenylalkyl pyridine orpyrazine (i.e. an alkyl-substituted pyridine or pyrazine moiety).

Such mixtures may comprise, for example, S-ethyl-Z- (4,8-dimethyl nona3,7-dienyl) pyridine; 2-(4,8-dimethyl-nona-3,7-dienyl) pyrazine and/or4(5,9-undecadienyl) pyridine. When mixtures of the C-10, C-ll, (1-12 andC-13 alkadienyl, cycloalkenyl, cycloalkylalkenyl, cycloalkylidenealkylor cycloalkenylalkyl pyridines and pyrazines are used, their proportionscan be varied as desired to suit the particular foodstuff to be flavoredand will depend upon whether the composition so formulated is utilizedto supply a total organoleptic impression or to enhance or fortify anexisting flavor and/ or aroma characteristic. It has been found whenpreparing spice or cinnamon flavors, for example, that a good blend isobtained by using a mixture of about -20% of at least one unsubstitutedC-12 alkadienyl pyridine e.g'. 2(2,4,8-trimethyl-3,7-nonadienyl)pyridine and/or 4(2,4,8-trimethyl-3,7- nonadienyl) pyridine; about40-50% of at least one C-1 1 alkadienyl pyridine having alkylsubstituents on the pyridine moiety, e.g.,2(4,7-dimethyl-3,7-nonadienyl)-4-propyl-pyridine;3-ethyl-4-(4,8-dimethyl 3,7 nondienyl) pyridine; and/or2-methyl-4-(4,8-undecadienyl) pyridine; about 1020% of at least onealkyl substituted (3-12 alkadienyl pyrazine, e.g.,2-methyl-4-(4,8-dodecadienyl) pyrazine and/or4-ethyl-4-(2,4,8-trimethyl-4,8-nondienyl) pyrazine; and about -30% of atleast one C-10 alkadienyl pyrazine, e.g., 3(3,7-decadienyl) pyrazine. Itwill be understood that these ratios can be varied to supply, enhance,modify or fortify the flavor of the foodstuff or flavoring composition.

The nature of the co-ingredients included with the alkadienyl,cycloalkenyl, cycloalkylalkenyl, cycloalkylidenealkyl orcycloalkenylalkyl heterocyclic nitrogen compound or compounds of thisinvention in formulating the product composition will, of course, dependprimarily upon the ultimate use contemplated, i.e., as a foodstuff perse or tobacco flavor per se, or alternatively as a flavoring compositionadapted to be added to a foodstuff or tobacco at some subsequent pointof time. In any event, such compounds serve to alter the organolepticcharacter- 16 istics of the ultimate foodstuiis or tobacco treatedtherewith.

Substances suitable for use herein as co-ingredients or flavoringadjuvants are well known in the art for such use being extensivelydescribed in the relevant literature. Apart from the requirement thatany such material be ingestibly" acceptable, and thus non-toxic orotherwise non-deleterious, nothing particularly critical resides in theselection thereof. Accordingly, such materials, which may in general becharacterized as flavoring adjuvants or vehicles comprise broadly,stabilizers, thickeners, surface active agents, conditioners, flavorantsand flavor intensifiers.

Stabilizer compounds included preservatives, e.g. sodium chloride,antioxidants, e.g., calcium and sodium ascorbate, ascorbic acid,butylated hydroxyanisole (mixture of 2 and 3 tertiarybutyl-4-hydroxyanisoles), butylated hydroxy toluene(2,6-di-tertiary-butyl-4-methyl phenol), propyl galla te and the like,and sequestrants, e.g. citric acid.

Thickener compounds include carriers, binders, protective colloids,suspending agents, emulsifiers and the like, e.g., agar-agar;carrageenan; cellulose derivatives such as carboxymethyl cellulose andmethyl cellulose; natural and synthetic gums such as gum arabic, gumtragacanth; gelatin, proteinaceous materials, lipids; carbohydrates;starches; pectins, and emulsifiers, e.g., monoand diglycerides of fattyacids, skim milk powder, hexoses, pentoses, dissacharides e.g., sucrose,corn syrup solids and the like.

Surface active agents include emulsifying agents, e.g., fatty acids suchas caprig acid, caprylic acid, palmitic acid, myristic acid and thelike, monoand diglycerides of fatty acids, lecithin, defoaming andflavor-dispersing agents such as sorbitan monostearate, potassiumstearate, hydrogenated tallow alcohol and the like.

Conditioners include compounds such as bleaching and maturing agents,e.g., benzoyl peroxide, calcium peroxide, hydrogen peroxide and thelike; starch modifiers such as peracetic acid, sodium chlorite, sodiumhypochlorite, propylene oxide, succinic anhydride and the like, buffersand neutralizing agents, e.g., sodium acetate, ammonium bicarbonate,ammonium phosphate, citric acid, lactic acid,

vinegar and the like; colorants, e.g. carminic acid, cochineal, tumericand curcinin and the like; firming agents such as aluminum sodiumsulfate, calcium chloride and calcium gluconate; texturizers;anti-caking agents, e.g., aluminum calcium phosphate; enzymes; yeastfoods, e.g., calcium lactate and calcium sulfate; nutrient supple ments,e.g., iron salts such as ferric phosphate, ferric pyrophosphate, ferrousgluconate and the like, riboflavin, vitamins, zinc sources such as zinchchloride, zinc sulfate and the like.

Flavorants and flavor intensifiers include organic acids, e.g., fattysaturated, unsaturated and amino acids; alcohols, e.g., primary andsecondary alcohols; esters, carbonyl compounds including aldehydes andketones, lactones; cyclic organic materials including benzenederivatives; alicyclics, heterocyclics such as furans, particularly3-acetylfuran, alkyl pyridines, alkyl and polyalkyl pyrazlnes and thelike, sulfur-containing materials including thiazoles, thiols; sulfides,disulfides and the like, so-called flavor potentiators such asmonosodium glutamate, tetramethyl pyrazine, guanylates, inosinates,natural and synthetic flavorants such as vanilliin, ethyl-vanillin,diacetyl, phenethyl-Z-furoate, maltol, natural gums and the like;spices, herbs, essential oils and extractives including bitternessprinciples such as theobromin, caifein, naringin and other suitablematerials creating a bitter effect.

The specific flavoring adjuvant selected for use may be either solid orliquid, depending upon the desired physical form of the ultimateproduct, i.e., foodstuffs, whether simulated or natural, and should, inany event, be capable of providing an environment in which the C-10,C-ll, C-l2 or C-13 alkadienyl, cycloalkenyl, cycloalkylalkenyl,

cycloalkylidenealkyl or cycloalkenylalkyl pyridine or pyrazine(s) can bedispersed or admixed to provide a homogeneous medium. In addition,selection of one or more flavoring adjuvants as well as the quantitiesthereof will depend upon the precise organoleptic character desired inthe finished product; thus, in the case of flavoring compositions,ingredient selection will vary in accordance with the foodstuffs towhich the flavor and aroma are to be imparted. In contra-distinction inthe preparation of solid products, e.g. simultated foodstutfs,ingredients capable of providing normally solid compositions should beselected such as various cellulose derivatives.

As will be appreciated by those skilled in the art, the amount of C-lO,C-ll, C-12 or C-13 alkadienyl, cycloalkenyl, cycloalkylalkenyl,cycloalkylidenealkyl and cycloalkenylalkyl pyridine and/ or pyrazineemployed in a particular instance can vary over a relatively wide rangewhereby to achieve desired organoleptic effects having reference to thenature of the product. All parts and percentages given herein are byweight unless otherwise specified. Thus, correspondingly greater amountswould be necessary in those instances wherein the ultimate foodcomposition to be flavored is relatively bland to the taste, whereasrelatively minor quantities may suflice for purposes of enhancing acomposition merely deficient in natural flavor or aroma. Thus, theprimary requirement is that the amount selected be effective, i.e.,suflicient to alter the organoleptic characteristics of the parentcomposition, whether foodstuff per se or flavoring composition.

Thus, the use of insuflicient quantities of the C-10, C-ll, C-12 or C-13alkadienyl, cycloalkenyl, cycloalkylalkenyl, cycloalkylidenealkyl orcycloalkenylalkyl pyridine or pyrazine will, of course, substantiallyvitiate any possibility of obtaining the desired results while excessquantities prove needlessly costly and in extreme cases, may disrupt theflavor-aroma balance, thus proving selfdefeating. Accordingly, theterminology effective amount and suflicient amount is to be accorded asignificance in the context of the present invention consistent with theobtention of desired flavoring effects. Thus, and with respect toultimate food compositions, it is found that quantities of C-10, C-ll,C-12 or C-13 alkadienyl, cycloalkenyl, cycloalkylalkenyl,cycloalkylidenealkyl or cycloalkenylalkyl pyridine(s) or pyrazine (s)ranging from a small but effective amount, e.g., 1.0 part per million upto about 200 parts per million by weight based on total composition aresuitable. Concentrations in excess of the maximum quantities stated arenot normally recommended since they fail to provide commensurateenhancement of organoleptic properties. In those instances wherein theC-lO, C-11, C-l2 or C-13 alkadienyl, cycloalkenyl, cycloalkylalkenyl,cycloalkylidenealkyl and/or cycloalkenylalkyl pyridine(s) or pyrazine(s)is (are) added to the foodstuff as (an) integral component(s) of aflavoring composition, it is, of course, essential that the totalquantity of flavoring composition employed be sufficient to yield aneffective C-lO, C-ll, C-12 or Cl3 alkadienyl, cycloalkenyl,cycloalkylalkenyl, cycloalkylideneallyl and/or cycloalkenylalkylpyridine or pyrazine concentration in the foodstuff product.

Favoring compositions or tobacco prepared in accordance with the presentinvention preferably contain the C-10, C-ll, C-l2 or C-13 alkadienyl,cycloalkenyl, cycloalkylalkenyl, cycloalkylidenealkyl and/orcycloalkenylalkyl pyridine or pyrazine in concentrations ranging fromabout 2.0 to 100% by weight, based on the total weight of said flavoringcomposition. The compositions described herein can be prepared accordingto conventional techniques well known in the art for such purposes.Thus, liquid products as typified by cake batters (e.g. yieldingcinnamon-tasting cakes) can be formulated by merely admixing theinvolved ingredients within the proportions stated in a suitable blenderto obtain the desired consistency, homogeneity of dispersion, etc.Alternatively, flavoring comopsitions in the form of the particulatesolids can be conveniently prepared by admixing the C-l0, C-ll, C-12 orC-13 alkadienyl, cycloalkenyl, cycloalkylalkenyl, cycloalkylidenealkyland/or cycloalkenyl alkyl pyridine(s) or pyrazine(s) with, for example,gum arabic, gum tragacanth, carrageenan and the like, and thereafter,spray drying the resultant mixture whereby to obtain the particulatesolid product. Pre-prepared flavor mixes in powder form, e.g., spice mixmay be obtained by mixing the dried solid components, e.g., groundparsley leaves, curry powder, korma and the like and the C-10, C-ll,C-12 or C-13 alkadienyl, cycloalkenyl, cycloalkylalkenyl,cycloalkylidenealkyl or cycloalkenylalkyl pyridine or pyrazine in a dryblender until the requisite degree of uniformity is achieved. It ispresently preferred to combine with the C-l0, C-ll, C-12 or C-13alkadienyl, cycloalkenyl, cycloalkylalkenyl, cycloalkylidenealkyl, orcycloalkenylalkyl pyridines or pyrazines of this invention the followingflavoring adjuvants: vanillin, 1(3,4,5-trimethoxy phenyl)propene-2,cinnamic aldehyde, eugenol methyl ether, and DL-methionine.

It is well known in the tobacco art that the domestic tobaccos which areexemplified by burley, Maryland, fluecured, bright leaf or Virginiatobaccos are low in flavor as compared with so-called oriental oraromatic tobaccos which are imported from Turkey, Greece, Bulgaria,Yugoslavia, Rhodesia, and Russia. Accordingly, it has been commonpractice in the tobacco industry to prepare blends of domestic andoriental tobaccos in order to provide cigarettes which have desiredflavor and aroma char acteristics. This invention also provides atobacco whi has an enhanced flavor and aroma.

With reference to the aspect of this invention which concerns tobaccoflavoring the C-lO, C-ll, C-12 and C-13 alkadienyl, cycloalkenyl,cycloalkylalkenyl, cycloalkylidenealkyl and/or cycloalkenylalkylpyridines and/or pyrazines of this invention are added to tobacco inamounts to provide generally a tobacco in which is dispersed about0.00005 to about 0.3 percent by weight of the additive. Preferably, theamount of additive is between about 0.0003 and about 0.02 percent byweight in order to provide tobacco having a desired flavor and aroma.The preferred percentages may be somewhat less, however, if otherflavorants imparting a desired aroma are also employed. The additivesmay be applied in any suitable manner and preferably in the form of aliquid solution or suspension by spraying, dipping or otherwise. Theadditives may be incorporated at any step in the treatment of tobacco,but are preferably added after aging; curing and shredding and beforethe tobacco is formed into tobacco products such as cigarettes, cigarsand the like. Likewise, it will be apparent that only a portion of thetobacco need be treated and the thus treated tobacco may be blended withother tobacco before the tobacco products are formed. In such cases, thetobacco treated may have the additives, in excess of the amounts aboveindicated so that when blended with other tobaccos the final productwill have the percentage within the indicated range.

In accordance with an example of this invention, an aged, cured andshredded domestic burley tobacco is sprayed with a one percent ethylalcohol solution of 4- (l,4,8-trimethyl-3,7-nonadienyl) pyridine in anamount to provide a tobacco composition containing 0.005 percent byweight of the said pyridine on a dry basis. Thereafter the alcohol isremoved by evaporation and the tobacco is manufactured into cigarettesby the usual techniques. The cigarette when treated as indicated has adesired and pleasing aroma which is detectable in the main and sidesmoke streams when the cigarette is smoked; this aroma is described bysome smokers as a woody cigar box-like note.

It will be particularly apparent that the manner in which the C-10,C-ll, C-l2 and C-13 alkadienyl-, cycloalkenyl, cycloalkylalkenyl,cycloalkylidenealkyl and/or cycloalkenylalkyl pyridines and/or pyrazinesare applied to the tobacco is not particularly important since, asindicated, it may be done in the form of spraying or dipping, utilizingsuitable suspensions or solutions of the additive.

Thus, water or volatile organic solvents, such as alcohol, ether,acetone, volatile hydrocarbons and the like, may be used as the carryingmedium for the additive while it is being applied to the tobacco Also,other flavor and aroma producing additives, such as those disclosed in Iones US. Pat. No, 2,766,145 and Schumacher U.S. Pat. No. 2,978,365, maybe incorporated into the tobacco with the additives of this invention.

While this invention is useful in the manufacture of cigarette tobacco,it is also suitable for use in connection with the manufacture of pipetobacco, cigars and other tobacco products formed from sheeted tobaccodust or fines which are well known to the art. Likewise, the additivesof the invention can be incorporated with materials such as filter tipmaterials, seam paste, packaging materials and the like which are usedalong with tobacco to form a product adapted for smoking Furthermore,the compounds can be added to certain tobacco substitutes of natural orsynthetic origin and by the term tobacco as used throughout thisspecification is meant any composition intended for human consumption bysmoking or otherwise, whether composed of tobacco plant parts orsubstitute materials or both.

The following examples serve to illustrate embodiments of the inventionas it is now preferred to practice it. It will be understood that theseexamples are illustrative and the invention is to be consideredrestricted thereto only as indicated in the appended claims.

EXAMPLE I Preparation of 2-(4,8-dimethyl-3,7-nonadienyl)pyridine Into a5-liter three-neck flask equipped with stirrer, thermometer, condenser,addition funnel, drying tube and gas bubbler are placed the followingingredients:

465 g. Z-methylpyridine (5 moles) 500 g. benzene At room temperature,with stirring, 200 g. of sodium amide are added. The temperature of thereaction mass is allowed to rise to 80-85 C. 807 g. of myrcenehydrochloride (3.5 moles) is added to the reaction mass over a period ofone hour while maintaining the temperature at 80 C. The reaction mass isthen stirred for three hours at 80 C.

On cooling, 100 cc. of water is slowly added. The reaction mass issubsequently poured into one liter of water and the organic layer isseparated and washed: first with a 300 cc. quantity of 5% aqueous sodiumhydroxide and then with two 300 cc. volumes of water. The solvent isstripped off the organic layer and the reaction product is rushed overat 2 m. Hg pressure and 130-140 C. The reaction product is thendistilled in a fractionation column at a temperature in the range of110-1l3 C. and a pressure of 0.7 mm. Hg. The fractions resulting fromthe distillation of the 2 (4,8-dimethyl-3,7-nonadienyl)pyridine havedistinct berry-fruit, woody-green and woodyamher notes. The followingformula is confirmed by NMR, mass spectral and IR analysis:

Using the foregoing procedure, when Z-methyl pyridine is replaced by2,4-dimethyl pyridine, a mixture of 4-rnethyl-2-(4,8-dimethyl-3,7-nonadienyl) pyridine and 2-methyl-4-(4,8-dimethyl-3,7-nonadienyl) pyridine is synthesized.

Using the foregoing procedure, when Z-methylpyridine is replaced byZ-methylpyrazine, as a starting reactant,

20 the compound: 2-(4,8-dimethyl-3,7-nonadienyl) pyrazine issynthesized.

EXAMPLE II Preparation of 4-(4,8-dimethyl-3,7-nonadienyl)pyridine Into a22-liter reaction flask equipped with stirrer, thermometer, additionfunnel, reflux condenser and gas bubbler are added the followingmaterials:

4,185 g. 4-methyl pyridine (45 moles) 3,600 g. benzene (anhydrous)Through an addition tube, over a period of twenty-five minutes, 1,802 g.(45.9 moles) of sodium amide are added, the temperature of the reactionmass being maintained at 2430 C. The reaction mas is then heated slowlyto reflux (pot temperature of 84 C.) and maintained at reflux until gasevolution ceases (4.5) hours). Over a period of 2.5 hours whilecontinuing refluxing 6,291 g. of myrcene hydrochloride is added. Thereaction mass is refluxed for three hours, maintaining the temperaturethereof at -94 C. When reaction ceases, the mass is cooled and pouredslowly over 9,000 g. of ice and water.

The aqueous phase is extracted with a 25-liter volume of benzene and theorganic phases are combined and washed with two 3.0-liter volumes ofwater. The solvent is then stripped off at mm. Hg pressure. The reactionproduct is rushed over at a vapor temperature of 52-159 C. (1-15 mm. Hgpressure). The reaction product is then fractionally distilled on a 12"Goodloe column at a temperature in the range 123-150 C., and a pressureof 2.4 mm. Hg [reflux ratio 1:1]. The reaction product has a refractiveindex of n =L5153 and a density at 25 C. of 0.9222. Infrared, NMR andmass spectral analysis indicates that the reaction product includes acompound having the structure:

The product has a highly desirable seashore aroma reminiscent of oceanspray.

EXAMPLE III The following composition is prepared:

Parts by weight Ingredient 275 Linalyl acetate. 135 Bergarnot oil. 135Citronellol.

135 Lavandulol. 40.5 Portugal oil. 20.5 Neroli oil. 20.5 Jasmin oil.28.0 Jasmin absolute. 28.0 Neroliol, Bigarade. 13.5 Rosemary oil.

4-(4,8-dimethyl-3,7 no-nadienyl) pyridine prepared by the process ofExample II.

13.5 Rose absolute.

l3.5 Hydroxy citronellol.

7.0 Cyclopentadecanolide 10%.

The addition of the 4-(4,8-dimethyl-3,7-nonadienyl) pyridine in thequantity given adds a distinct seashore aroma to the fragrance. In theinstant example, the 40.5 parts of neroli oil can be replaced by 20parts of 2-( 1,4,8- trimethyl-3,7-nonadien-1-yl)pyridine of thisinvention (as 21 prepared by the process of Example VII herein) withoutchanging the olfactory nature or quality of the fragrance.

EXAMPLE IV The composition of Example III is incorporated in a colognein a concentration of 2.5% in 85% ethanol; and into a handkerchiefperfume in a concentration of 20% (in 95% ethanol). The compoundsproduced in Example II afford a distinct and definite seashore aroma,reminiscent of ocean spray to the handkerchief perfume and cologne.

EXAMPLE V Synthesis of -ethyl-2- (4,8-dimethyl-nona-3,7-dienyl) pyridine(E and Z) Into a 5-liter reaction flask equipped with stirrer,thermometer, addition funnel, reflux condenser, outlet bubbler, wet testmeter and heating mantle are added the following materials: 184 gramssodium amide, and 1080 ml. anhydrous benzene.

The benzene-sodium amide mixture is heated at refiux at 81 C. Over aperiod of one hour, 508 grams of S-ethyl- Z-picoline is added whilerefluxing the mixture at a temperature of 81-91" C. Over a period of 4hours, 1120 grams of myrcene hydrochloride is then added during whichtime ammonia gas is evolved. When the ammonia gas evolution ceases, oneliter of a saturated sodium chloride solution and 400 ml. of water isadded to the reaction mass. The aqueous layer is then separated and theorganic layer is first rushed over and then subjected to distillationover a temperature range of 155160 C. (pressure: 2.5 mm. Hg). The yieldof purified material resulting from subsequent distillation [143-149 C.(1.4- 1.5 mm. Hg)] On a Goodloe column is 460 grams. On the basis of NMRanalysis the product is a mixture of cis (E) and trans (Z) isomershaving the following structures:

The mixture has a green, fresh potato aroma. At concentrations of 50p.p.m. in water the product exhibits a coriander-oil-like aroma.

EXAMPLE VI Process for the preparation of 4-1(l,4,8-trimethyl-(E)-3,7-nonadien-l-yl pyridine and 4-(l,4,8-trimethyl-(Z)- 3,7-nonadien-1-ylpyridine Into a 2-liter reaction flask equipped with stirrer,thermometer, dropping funnel, condenser, outlet buttler, wet test meterand heating mantle are added the following ingredients: 90 grams sodiumamide, and 380 ml. anhydrous benzene.

The mixture is heated to reflux (80 C.) and to the refluxing mixture 240grams of 4-ethyl pyridine are added over a period of eight hours. Over aperiod of six hours while refluxing, 360 grams of myrcene hydrochlorideis then added. During this period of time ammonia gas is evolved. At thecessation of evolution of ammonia gas, the reaction mixture is washedwith one liter of saturated sodium chloride solution and 500 ml. ofWater. The reaction mass is then separated into a aqueous phase (whichis discarded) and an organic phase which is distilled at a vaportemperature in the range of 128139 C. (pressure: 1.01.5 mm. Hg). Theyield of the material thus recovered is 218 grams. The resultingmaterial has a chem- 1cal structure confirmed by NMR as follows:

The material has a strong persistent amber-woody note.

EXAMPLE VII Preparation of 2-( 1 ,4,8-trimethyl-(E)-3,7-nonadien-l-yl)pyridine and 2-(l,4,8-trimethyl (Z)-3,7-nonadien-l-yl) pyridine gas isevolved. At the cessation of evolution of ammonia gas, the reactionmixture is washed with one liter of saturated sodium chloride solutionand 500 m1. of Water. The reaction mass is then separated into anaqueous phase (which is discarded) and an organic phase which isdistilled at a vapor temperature in the range of 124427 C. (pressure:1.7-1.8 mm. Hg). The yield of the material thus recovered is 218 grams.The resulting material has a chemical structure confirmed by NMR asfollows:

The product has spice-like and woody flavor notes and a green and twiggyaroma.

EXAMPLE VIII The following composition is prepared (parts by weight):

Ingredient: Parts Bergamot oil 120 Methyl ionone 60 Jasmin extraPetitgrain 60 Patchouli oil 60 Violet perfume base 605-ethyl-2-(4.8-dimethylnona 3,7 dienyl)pyridine (E and Z) Lemon oil 80Rose Geranium oil Lavender oil, French 120 Sweet Orange Oil 80 Muskextract, 3% 50 Civet extract, 3% 50 The addition of5-ethyl-2-(4,8-dimethyl-nona-3,7-dienyl)pyridine (E and Z) improves theoverall quality of the instant formulation, lending a more nerolioil-like and a coriander-like effect thereto.

23 EXAMPLE IX The composition of Example VIII is incorporated into acologne in a concentration of 2.5% in 85% ethanol and into ahandkerchief perfume in a concentration of 20% (in 95% ethanol). Theproduct of Example V affords a distinct and definite neroli oil-like andcoriander like quantity to the handkerchief perfume and cologne.

The mixture is refluxed for four hours, cooled and then 10.28 parts of95% alcohol are added. The reaction product is aged for three days andthen 1.14 parts of S-ethyl- 2-(4,8-dimethyl-nona-3,7-dienyl) pyridine (Eand Z) as prepared in Example V are added. The resulting product is anexcellent potato flavor with an intense green note.

The resulting product can be further processed to a dry powder byadmixing 100 parts with 28 parts of gum arabic. The mixture isemulsified and spray-dried to produce a dry powder which is suitable foruse as a potato flavor on'dried materials or which can be redissolved inwater or other vehicles for deposition from a solution, suspension oremulsion.

Another excellent potato flavor is prepared, having a still more intensegreen note when the material of Example V is replaced by the material ofExample VII.

EXAMPLE XI A perfume composition is prepared with the followingingredients:

A perfume composition exhibits an excellent woody fragrance. When thealkadienyl pyridine of Example V1 is omitted, the composition lacks thewoody, amber fullness of the complete perfume composition of thisexample.

It will be understood from the present description that the 1,5,8- and1,6,8-trimethyl homologues of the materials prepared in Example VI ofthe present invention can be used separately or in combination with eachother to provide a good intense amber, woody fragrance note.

EXAMPLE XII Preparation of soap composition One hundred grams of soapchips are mixed with one gram of the perfume composition of Example XIuntil 24 a substantially homogeneous composition is obtained. Theperfumed soap composition manifests an excellent woody, amber, odorcharacter.

EXAMPLE XII Preparation of a detergent composition A total of grams of adetergent powder is mixed with 0.15 gram of the perfume composition ofExample XI until a substantially homogenous composition is obtained.This composition has an excellent woody-amber odor.

EXAMPLE XIV Preparation of a cosmetic powder composition A cosmeticpowder is prepared by mixing in a ball mill 100 grams of talcum powderwith 0.25 gram of the mixture obtained from the process of Example VI. Asecond cosmetic powder is similarly prepared except that the material ofExample I is used. The cosmetic powders prepared using the Example VImixture and the Example I material have excellent woody-amber aromas.

EXAMPLE XV Perfumed liquid detergent EXAMPLE XVI Into a 2-liter flaskequipped with stirrer, thermometer, condenser, dropping funnel, heatingmantle, outlet bubbler and wet test meter the following ingredients areadded:

Sodium amide g 150 Alpha-picoline g 348 Anhydrous benzene mls 375 Theforegoing mixture is heated to reflux and over a period of one hour, 600grams of myrtenyl chloride is added causing the evolution of 76 litersof ammonia gas. At the termination of the reaction the reaction mass iswashed with two 500 ml. volumes of a 10% sodium chloride solution, theaqueous layer is separated from the organic layer and discarded. Theorganic layer is rushed over under vacuum and then distilled at atemperature in the range of -126 C. [1.7-1.8 mm. Hg] in a one-footGoodloe distillation column operating at a reflux ratio of 9:1. Theresulting product as determined by NMR analysis is2-(2-pinen-10-yl-methyl)pyridine having the structure:

The material has a fresh green verdural type odor with animal, amber andseashore aroma-like qualities.

EXAMPLE XVII Preparation of a perfume composition containing2-(2-pinen-10-yl-methyl) pyridine The following composition is prepared:

Parts by Weight: Ingredient 135 Linalyl acetate. 275 Bergamot oil. 135Citronellol.

135 Lavandulol. 135 Portugal oil. 40.5 Neroli oil. 20.5 Jasmin oil. 20.5Jasmin absolute. 28.0 Neroliol, Bigarade. 28.0 Rosemary oil. 23.5 2 2Pine-lO-yl-methyl) pyridine prepared by the process of Example XVI.

13.5 Rose absolute. 13.5 Hydroxy citronellol. 7.0 CyclopentadecanolideThe addition of the 2-(2-pinen-10-yl-methyl) pyridine in the quantitygiven adds an excellent distinctive ambery seashore aroma to thefaagrance.

EXAMPLE XVIII Preparation of 4-(2-pinen-10-yl-methyl) pyridine Into atwo-liter flask equipped with stirrer, thermometer, condenser, droppingfunnel, heating mantle, outlet bubbler and Wet test meter the followingingredients are added:

Sodium hydride (57% in mineral oil) g 100 Toluene, anhydrous 1nls 540Gamma-picoline g 205 The mixture is heatd to reflux (117 C.) andmaintained at reflux until gas evolution ceases (thus forming a picolinesalt product). Into a 3-liter flask equipped with stirrer, thermometer,condenser, dropping funnel, ice bath, outlet bubbler and wet test meter500 gm. of myrtenyl chloride is added. While maintaining the temperatureof the reaction mixture at 2427 C. (with the use of an ice bath) thecontents produced as described above, in the 2-liter flask (comprisingthe picoline salt product) are added over a period of four hours. Thereaction mixture is then admixed with one liter of a saturated sodiumchloride solution followed by admixture with 250 ml. of Water. Theaqueous phase is separated and discarded and the organic phase is rushedover and then distilled at a temperature range of 128130 C. (1.21.3 mm.Hg] in a 6" Goodloe distillation column, operating at a reflux ratio of1:1. The reaction product as determined by NMR analysis is4-(2-pinen-10-ylmethyl)pyridine having the structure:

This material has a woody odor with seashore and citrus notes.

26 EXAMPLE XIX Preparation of perfume composition containing 4-(2-pinen- 10-yl-methyl) pyridine The following composition is prepared:

The addition of the 4-(Z-pinen-l0-yl-methyl)pyridine in the quantitygiven adds an excellent, distinctive, woody, citrusy seashore aroma tothe fragrance.

In the instant example, the 40.5 parts of neroli oil can be replaced by20 parts of 2-(1,4,8-trimethyl-3,7-non adien-l-yl)pyridine of thisinvention (as prepared by the process of Example VII herein) Withoutchanging the olfactory nature or quality of the fragrance.

EXAMPLE XX The following mixture is prepared:

Ingredient: Parts by weight Diacetyl (10% in ethanol) 2 2,3-diethylpyrazine (1% in ethanol) 4 Furfural 6 Methional (10% in ethanol) 4Phenyl acetaldehyde (10% in ethanol) 2 5 ethyl 2 (4,8 dimethyl 3,7nonadienyl) pyridine as prepared in Example V. [10% in ethanol] 4 Maltoll Tetramethyl pyrazine (1% in ethanol) 2 ethanol 15 Propylene glycol 60The C-ll alkadienyl pyridine prepared by the process of Example V addsto the formulation an excellent raw fresh potato character.

EXAMPLE XXI One mole of a-pyridyl magnesium chloride-tetrahydro furancomplex (prepared by the process of Example 17 at column 16 of US. Pat.2,855,397) dissolved in tetrahydrofuran (total volume: 442 ml.) is addedslowly from a dropping funnel to a stirred mass of 1 mole of 6,6-dimethyl-norpinane-2-acetaldehyde (prepared by the process described atcolumns 5 and 6 of US. Pat. 2,427,345) in a one liter flask equippedwith thermometer, nitrogen bubbler, heating mantle and reflux condenser.Air is displaced from the apparatus by nitrogen, a slow flow of this gasbeing maintained during the reaction. The temperature of the reactionmixture is maintained at about 40 C. by varying rate of addition of theot-pyridyl Grignard reagent and by occasional use of a cooling waterbath and heating mantle, alternately. The reagent is added over a thirtyminute period, the stirring of the reaction mass being continued for anadditional 2.5 hours. Then, dilute sulfuric acid (28 ml. in ml. Water)is slowly added. GLC, mass spectral, infra-red and NMR analysis yieldthe information that the product thus formed has the structure:

! 1 l HO O as confirmed by NMR and Infra-red analysis.

0.1 mole of the resulting product, dissolved in glacial acetic acid ishydrogenated in a low pressure hydrogenator with 100 mg. of Adamscatalyst for 1.5 hours. Pressure drop vs. time charting shows when thehydrogenation is complete. Fractional distillation of the resultingmaterial at 125-127 C. (1.7-1.8 mm. Hg) yields a reaction product havingthe structure:

confirmed by NMR and infra-red and Raman spectral analysis.

EXAMPLE )QIII Into a one-liter round-bottom flask equipped with refluxcondenser, stirrer, gas-inlet tube and dropping funnel are placed thefollowing ingredients:

Lithium gm 7.4 Diethyl ether cc 300 50% bromobenzene-diethyl ethersolution cc 20 A mixture of 61 cc. of 2,4-dimethyl-pyridine and 60 cc.of diethyl ether is added, with stirring over a period of one hour. Theflask is then cooled in an ice-NaCl bath, and a solution of 60 gm. ofmyrtenal in 60 cc. of diethyl ether is added over a period of two hours.The reaction mass is then poured onto ice and extracted with two volumesof diethyl ether. The resulting ether layer is then extracted with anexcess of ice-cold 1 N HCl. Then, an excess of ice-cold 2 N NaOHsolution is added to the acidic solution and the liberated alcohol isdissolved in ether. After washing with water, drying with sodium sulfateand removal of the ether by distillation, the residue is distilled inhigh vacuum yielding a product (confirmed by NMR and IR analysis) havingthe structure:

The resulting product is dehydrated and hydrogenated according to theprocedure set forth in Example XXI, thus yielding a compound having thestructure:

as confirmed by NMR, infrared and mass-spectral analysis.

It will be appreciated from the present description that the novelheterocyclic nitrogen compounds can be included in other flavoring orperfume compositions and in other foodstuffs, tobacco compositions orperfumed articles.

What is claimed is:

1. A nitrogen heterocyclic compound having the structure:

omrtQ wherein R represents C -C lower alkyl and m is an integer rangingfrom zero up to 2; wherein one of A or A is a moiety selected from thegroup consisting of cyclododecen-3-yl-methyl,

2-pinen-l0-yl-methyl, 4,8-dimethyl-3,7-nonadienyl,S-methyl-6-i-propyl-2-cyclohexenyl-rnethyl, and1,4,8trimethyl-3,7-nonadien-1-yl,

and the other of A or A is R or hydrogen.

. 4-{2-pinen-lO-yl-methyl) pyridine.

. 2-(2-pinen-10-yl-methyl) pyridine.

A (4,8-dimethyl-3,7-nonadienyl) pyridine.

. 2(4,8-dimethyl-3,7-nonadienyl)pyridine.

4(4,8-dimethyl-3,7-nonadienyl) pyridine.

. 2-ethyl-5-(4,8-dimethyl-3,7-nonadienyl) pyridine.

2(1,4,S-trimethyl-3,7-nonadienyl) pyridine.

. 4(l,4,8-trimethyl-3,7-nonadienyl) pyridine.

References Cited Karrer: Organic Chemistry, 4th English edition, p. 928,Elsevier Pub. Co. (N.Y.) 1950.

ALAN L. ROTMAN, Primary Examiner US. Cl. X.R.

260-240 D, 240 R, 250 R, 297 R, 297 B; 99-140 R; 424250, 263

